Anthraquinone derivatives and process of making same



Patented Feb. 10,1931

' UNITED sr rs PATET QFFICE;

FRANZ ACKERMANN, or BINNINGEN, NEAR BASEL, AND CARL APOTHEKER, orA'RLES- HEIM, NEAR Basra, sWrrZEnLAnn, Assrenoss To DUSTRY IN ,IBASLE,or BASEL, SWIT ERLAN ANTHRAQUINONE DERIVATIVES AND rnocnss or MAKINGSAME The present invention relates to the manufacture of newanthraquinones-derivatives which are valuable forthe productiOIl of fasttints on'the fiber; It comprises the process of making these newproducts, the new products themselves, and the material that has beendyed therewith. V

By carefully converting the products of the general formula 4 V a:NlIR'i wherein win one case stands for a nitro-group, and in the othercase for an NHR group and R stands for alkyl or hydrogen, Withprimaryaromatic or hydroaromatic amines, there. are obtained compounds of thegeneral formula Y It has now been found that these products may byreduction be converted into new com:v

pounds of .the general formula,

i z N HR! I NHR: wherein 'w'in onecase'standsfor NH gmup,:.and.ain-the:other case for an NHRL Il'oDrawing; Application fil'edDecember 19, 1929,Serial No. 415,353, and in Switzerland December 29, 1928.

group, R stands for alkyl or hydrogen,

R for an aromatic or hydroaromatic' residue;

These products are valuable dyestufis which, inter alia, dye'colloids-ofcellulose,

such as acetyl or alkyl cellulose, or nitroceL- lulose varnishes, fastblue to blue-greentints.

They form dark powders and dissolve-in or 1 solutions.

' By a suitable further treatment, for in stance by alkylatio'n; forexample with compounds, such as alkyl esters of the aromatic sulfonicacids, alkyl halides, such-as chloror methyl or ibromomethyl orcorresponding ethyl=derivatives, alkylenehalides, alkylene chlorhydrinsand alkyleneoxides, sulfona; tion, or acidylatiomfor QXMnplWith aceticanhydride' or befIlZQylchloride, or by successive alkylation andsulfonation, the new dye- SOCIETY or CHEMICAL stufls may be convertedinto further dye stufiswhich, acco rding to their constitution, haveafiinity forcol-loids of the cellulose series orf or the animal fiber.

Amongfthese products those are particularly'yaluable which areobtaine dby further alkylation, particularly with such alkylatingia'gentswhich'introducel methyl or-ethyl They c r e po d; with the g ne formulaR HN 0 NEE.

whe in a; "a, and R, send for an w sidues'of which at l a t. one' dn ansnotmo The following examples illustrate the invention, the parts beingby weight 5 E trample 1 10 parts of the reaction product obtained at 15O'16O C. from aniline and a technical mixture of 1: 5-diamino- 1:8-dinitroanthraquinone and 1 S-diamino-l: 5-dinitroanthraquinone, whichhas preferably been freed as far as possible from the ,8-isomerides, andwhichcorresponds to the formulae i and 250 parts of alcohol, 250 partsof water and 25 parts of calci'ned'sodium sulfide are heated together toboiling for 4- hours in a reflux apparatus. The cooled mixture isfiltered and the solid matter washed and dried. The reduction may alsobe carried out in water or alcohol alone. 1 i

I The dark powder thus obtained corresponds with the formula Hm N112line in beautiful blue laminae melting at 206 C. and which dyes acetatesilk blue-green tints.

By heating 10 parts of 1:5-diamino-4-nitro-8-phenylamino anthraquinoneat 135- 140 (1., while stirring, with 100 parts'of hexa-hydroaniline,the 1:5-diamino-4-hexahydroanilido-8-phenylamino anthraquinone separateson cooling'as a blue-black crystalline product. From aniline beautifulblue.- violet crystals are obtained which meltat 270 C. and dissolve inalcohol and pyridine to a blue solution.-

Example 2 p r 10 parts of 1:5-diainino- 1:S-dinitro-anthraquinone areheated with 25 parts of para- 7 anisidine and 50 partsortho-dichlorobenzene anisidino-anthraquinone are stirred inea refluxapparatus for hour with 80 parts of alcohol. There are thenadded 20parts of finely pulverized sodium liydrosulfide and the whole is keptunder reflux during 4 hours. The 11:5-triamino-8-para-anisidinc-anthraquinone separates in blue "violetcrystals which melt at 220 C. and dye acetate silk green-blue tints.Thesame product is also obtained from 1:8-diamino-4-nitr0-5-para-'anisidino-anthraquinone' From 1 5-diamino-4 :8-dinitro-anthraquinoneand para-toluidine there is obtained at 150155 C. the 15-diamino-4-nitro-8-paratoluidino-anthraquinone melting at 288290 (l;the reduction product thereof melts at 201? C. and dyes acetate silkgreen-blue. With ortho-anisidine there is obtained at 160165 C. the 1:5-diamino-1-nitro-8-orthoanisidino-anthraquinone; with hexa-hydroanilineat 95100 C. the 1: 5-dia1nino-4- nitro 8-hexa hydroanilidoanthraquinone; with para-chloro-aniline at 160-165 C. the 1 5 diamino 4Lnitro 8,-para-chloro-anilidoanthraquinone; with para-cresidine-methylether at 140-150 O. the 1: 5-diamino-4-nitro- 8-para-cresidine-methylether anthraquinone. Further condensation products are obtained withaand ,B-naphthylamine, the am ino-naphthol-ethers, amino-diphenyl, etc.

The reduction products of these substances dye nitrocellulosev varnishesblue to green tints.

Example 3 17 parts of the product of the reduction named in Example'lare stirred with 1500 parts of nitrobenzene at 100 C. There are thenadded 6 parts of. dimethylsulfate and the temperature is maintained atthe above degree'for 12 hours. After-cooling the whole is filtered,thesolid matter washed, dried and if necessary further purified'byre-dissolu- 10 parts of 1:5-diamino-4c nitro-8-para- I tion (for examplefrom'aniline or alcohol).

The dyestufi may also be isolated by adding to the mixtureofnitroben'zene and dyestuif without filtering it, sodium carbonatesolution and then distilling with steam. The new dyestuff dyes acetatesilk blue-green tints of great purity. l

. Further alkylating products are-obtained substituting other alkylatingagents,.jsuch,

as propionyl chloride, butyl, amyl or allyl halides, for thedimethylsulfate.

,Ewample 4 10 parts of 1:4:5-triamino-8-phenylamino-anthraquinone arestirred at 5055 C.

with 500 parts of alcohol and 100 parts of water. Into this solution aslow current of ethylene oxide is passed for 4 hours. On evaporation ofthe alcoholic solution a blue product is separated which dyes acetatesilk green-blue tints.

Example parts of l 1: 5-triamino-8-para-toluidoanthraquinone are stirredfor 2 to 3 hours at water-bath temperature with parts of monohydrate. Oncooling and precipitation with ice a dark blue powder is obtained whichcompletely dissolves in alkalies to a blue solution. green tints. Aproduct dyeing similar tints is obtained by sulfonating the 1 :45-triamino- 8-phenylamino-anthraquinone.

Example 6 7 10 parts of 1 :4 :5-triamino-8 phenylamino-' anthraquinoneare stirred at ISO-185 C. with RsHN ti 7 N HRz whereinR R and R standfor hydrogen or alkyl, and R for an aromatic or hydroaromatic residue,which product form dark powders which dissolve in alcohol or aniline toblue to green solutions, dyeing acetate silk and nitrocellulosevarnishes equal tints.

the compounds of the 2. As new products general formula I NHR1 I V I NHR:

wherein m in one case stands for an NH group and in the other case foran NHR group, R stands for alkyl or hydrogen, R

for an aromatic or hydroaromatic residue,

It dyes wool from an acid bath which products arm dark ea-eta whichdissolye in alcohol or aniline to blue tobluegreen solution's and' dyeacetate silk-andnitrocellulose varnish like tint-s." I

3. As new products the compounds ofthe n al formul I "a-ge'fuua whereinm in one case stands for an NH group and in'the other case for an NI-IRgroup, R stands for alkyl or hydrogen, and R for an aromatic residue,which products form dark powders which dissolve in alcohol or aniline toblue to blue-green solutions and dye acetate silk and nitrocellulosevarnish like tints. I

4. 'As new products the compounds of the general formula V I o NHR1wherein w in one case stands for an NIL- group and in the other case foran NHR group, R stands for alkyl' or hydrogen, and R for an aromaticresidue of the benzene series, which products form dark powders whichdissolve in alcohol or aniline to blue to blue-green solutions and dyeacetate silk and nitrocellulose varnish like tints. I

5. As new products the compounds of the general formula NHR1 O NHRIwherein m in one case stands for an NH group and 1n the other case foran NHR group, R stands for hydrogen or an alkyl 1 radical which containsnot more than two carbon atoms, and R stands for an aromatic residue ofthe benzene series, which products form dark powders which dissolve inalcohol or aniline to blue to blue-green solutions and dye acetate silkand nitrocellulose varnish like tints.

6. Material dyed with the products of 7 claim 1.

7 Material dyed with the products of claim 2. I

8. Material dyed with the products of claim 3.

9. Material dyed with the products of claim 4. a c

10. Material dyed with the products of claim 5. In Witness whereof Wehave hereunto signed our names this 9thday of December, 1929. e e eFRANZ AOKERMANN. CARL APOTHEKER.

